JPH0939103A - Decorative laminated sheet and decorative molded article manufacturing method - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To obtain a decorated molded article which is excellent in adhesion of the decorative laminated sheet to the molded article and is also excellent in hot water resistance. SOLUTION: A decorative base material is impregnated with a thermosetting resin composition containing an inorganic filler and a coupling agent, or
It is a decorative laminating sheet in which a decorative base material is impregnated with a thermosetting resin composition containing an inorganic filler surface-treated with a coupling agent. It is a method for producing a decorative molded product, which comprises performing heat compression molding using the decorative laminated sheet having this structure. Further, as the thermosetting molding material, a thermosetting resin composition containing a coupling agent is used, or as the thermosetting molding material, a thermosetting resin composition containing a coupling agent is used, and A method for producing a decorative molded article, which uses a decorative laminate sheet obtained by impregnating a decorative base material with a thermosetting resin composition containing a coupling agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a decorative laminating sheet and a molding material by placing a decorative laminating sheet and a thermosetting molding material in a molding die so as to overlap each other and performing heat compression molding. TECHNICAL FIELD The present invention relates to a method for producing a decorative molded product that exhibits a design property such as a desired pattern and color by a decorative laminating sheet, and a decoration used to obtain such a decorative molded product. It relates to a laminating sheet.

The decorative molded product thus obtained is suitably used for products having a pattern or color on the surface, such as bathtubs, wall materials for bathtubs, waterproof pans and counters.

[0003]

2. Description of the Related Art Conventionally, FRP (fiber reinforced plastic)
In the field of, especially in the production of FRP bathtubs, bath unit floors, etc., the method called hand lay-up molding method or spray-up molding method has been widely adopted, but these methods produce one product. It took a long time and a lot of work. Then, as a thing that greatly improves these productivity, sheet molding
A thermosetting molding material such as a compound (hereinafter abbreviated as SMC) or a bulk molding compound (hereinafter abbreviated as BMC) has been developed, and a heat compression molding method using the thermosetting molding material is currently widely used.

However, in the heat compression molding of SMC or BMC using only the thermosetting molding material, the color of the entire molded article is limited to a single color. The only problem is that only red ones can be produced, and the freedom of patterns and colors is narrowed. Of course, if post-processing such as printing or painting is performed on the molded product, it is possible to add patterns or colors as appropriate, but in this case it is necessary to add complicated post-processing steps, which further increases productivity. descend.

Therefore, as a method of decorating these FRP products, a method of using a decorative laminating sheet for expressing a desired pattern in a molded product has been proposed. For example, in Japanese Unexamined Patent Publication No. 5-285973, SMC is stacked on a decorative laminating sheet obtained by impregnating a titanium paper on which a desired pattern is printed with a thermosetting resin, and heat compression molding is performed. A method for obtaining a decorative molded article is disclosed.

The thermosetting resin composition used for such a decorative laminated sheet contains alumina powder and silica for the purpose of improving the wear resistance of the product or adjusting the gloss. Those to which an inorganic filler such as powder is added are used in applications where abrasion resistance is required.

[0007]

However, since the molded article obtained by the above-mentioned heat compression molding method is one in which the decorative laminating sheet is simply laminated on the surface of the molded article, Adhesion of the decorative laminating sheet to the molded product is poor, and for example, when the decorative laminating sheet is exposed to hot water for a long time, the decorative laminating sheet portion is easily peeled off from the molded product.

When a decorative laminated sheet containing an inorganic filler is used, the molded article obtained by the above method is also inferior in hot water resistance, and when it is exposed to hot water for a long time. There is a problem that the surface of the decorative laminating sheet is discolored white.

The present invention has been made to solve the above-mentioned drawbacks, and in forming a decorative laminated sheet laminated molded product having a design such as a free pattern, a color, etc., it is a molded product of the decorative laminated sheet. It is an object to provide a method for producing a decorated molded article which is excellent in adhesiveness to, and is also excellent in hot water resistance, and a decorative laminated sheet used for obtaining such a good decorative molded article. To do.

[0010]

DISCLOSURE OF THE INVENTION The present invention is to improve the above-mentioned drawbacks. In the invention of claim 1, a thermosetting resin composition containing an inorganic filler and a coupling agent is used as a decorative substrate. The decorative laminated sheet is characterized by being impregnated.

Further, the invention according to claim 2 is characterized in that a decorative base material is impregnated with a thermosetting resin composition containing an inorganic filler surface-treated with a coupling agent. It is a sheet.

According to the third aspect of the present invention, when the decorative laminating sheet is placed on the thermosetting molding material in a laminated form and the molding material is subjected to heat compression molding, the decorative laminating sheet is used as the decorative laminating sheet. 2. A method for producing a decorated molded product, characterized in that the product described in 2 is used.

According to a fourth aspect of the present invention, when the decorative laminating sheet is placed on the thermosetting molding material in a laminated form and the heat compression molding of the molding material is performed, a coupling agent is used as the thermosetting molding material. A method for producing a decorated molded article, which comprises using a thermosetting resin composition containing:

According to a fifth aspect of the present invention, a cup is used as a thermosetting molding material when the decorative laminating sheet is laminated on the thermosetting molding material and the molding composition is subjected to heat compression molding. A thermosetting resin composition containing a ring agent is used, and a decorative laminate sheet is obtained by impregnating a decorative base material with the thermosetting resin composition containing a coupling agent. The method for producing a decorated molded article is as follows.

First, the invention according to claim 1 will be described in detail.

In the present specification, the "decorated base material" means a base material decorated by printing or coloring.

Examples of the above-mentioned base material, that is, an undecorated base material include fiber aggregates such as paper, cloth, non-woven fabric, glass mat and glass cloth, and porous synthetic resin sheets.

As the paper, various conventionally known papers are used. Specifically, thin paper, titanium paper, newspaper roll paper, high-quality paper, medium-quality paper, waste paper, gravure paper, art paper, coated paper, writing paper, drawing paper, etc. can be used. As the printing method, various conventionally known methods can be applied, and specifically, there are a gravure printing method, a gravure offset printing method, a silk screen printing method, a letterpress printing method, an offset printing method and the like. Further, as a coloring method, various conventionally known methods can be applied, and specifically, there are a method of mixing a pigment and the like at the time of paper making, a method of impregnating ink at the time of paper making, a method of applying paint or a paint.

As the cloth, various conventionally known cloths are used. Specifically, natural fibers such as silk, hemp, and cotton,
It is possible to use those obtained by weaving recycled fibers such as rayon fibers, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers. As the printing method, various conventionally known methods can be applied, and specifically, there are a gravure printing method, a gravure offset printing method, a silk screen printing method, a letterpress printing method, an offset printing method and the like. Further, as a coloring method, various conventionally known methods can be applied. Specifically, a method of weaving using a fiber dyed with a dye, a method of impregnating cloth with ink or the like after weaving, a paint There is also a method of applying a paint to a cloth.

As the non-woven fabric, various conventionally known ones are used. Specifically, natural fibers such as silk, hemp, cotton and wool, regenerated fibers such as rayon fibers, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers are chemically or thermally bonded or bonded to each other. It is possible to use a cloth-like material that is made by welding or the like. As the printing method, various conventionally known methods can be applied, and specifically, there are a gravure printing method, a gravure offset printing method, a silk screen printing method, a letterpress printing method, an offset printing method and the like. Further, as a coloring method, various conventionally known methods can be applied, specifically, a method of forming a cloth by using a fiber colored with a dye, a method of impregnating an ink after forming the fiber into a cloth shape. , There is a method of applying paint or paint to a non-woven fabric.

As the above-mentioned glass cloth, a conventionally known one obtained by weaving glass fibers can be used. Also,
As the printing method, various conventionally known methods can be applied, and specifically, the gravure printing method includes a gravure offset printing method, a silk screen printing method, a relief printing method, an offset printing method, and the like. Also, as the coloring method, various conventionally known methods can be applied, specifically, a method of weaving using a fiber dyed with a dye, a method of impregnating glass cloth with ink or the like after weaving, There is a method of applying paint or paint to the glass cloth.

As the glass mat, it is possible to use a glass mat which is chemically bonded to glass fibers with an adhesive (binder) to form a mat. As the printing method, various conventionally known methods can be applied, and specifically, there are a gravure printing method, a gravure offset printing method, a silk screen printing method, a letterpress printing method, an offset printing method and the like. Further, as a coloring method, various conventionally known methods can be applied, specifically, a method of forming a mat by using fibers colored with a dye, a method of impregnating a glass mat with ink or the like after weaving. , There is a method of applying paint or paint to the glass mat.

Here, as a mode of coloring or printing,
It may be colored in a single color or a pattern such as a pattern may be formed by using a plurality of colors. That is, it is possible to apply a free pattern or color according to the purpose.

The thermosetting resin composition with which the decorative base material is impregnated contains a thermosetting resin as a main component and also contains an inorganic filler and a coupling agent.

As the thermosetting resin which is a main constituent of the thermosetting resin composition, various thermosetting resins such as unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin, diallyl phthalate resin, melamine resin and phenol resin can be used. Resin can be used.

The above-mentioned unsaturated polyester resin is usually produced by a known and commonly used method, usually an organic polyol, an aliphatic unsaturated polycarboxylic acid and, if necessary, an aliphatic saturated polycarboxylic acid and / or an aromatic polycarboxylic acid. Manufactured from etc.

Examples of the organic polyol used for producing the above unsaturated polyester resin include diol, triol, tetraol and a mixture thereof.
Organic polyols are mainly divided into aliphatic polyols and aromatic polyols, and of these, typical aliphatic polyols include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, dibromoneopentyl. Glycol, hexamethylene glycol, trimethylolpropane, hydrogenated bisphenol A, and the like. Typical aromatic polyols are bisphenol A or bisphenol S, or these bisphenol A or bisphenol S with ethylene oxide, propylene oxide, or butylene. Polyoxyalkylene bisphenol A or polyoxyalkylene bisphenol A obtained by adding an average of 1 to 20 aliphatic oxirane compounds such as oxides in one molecule There is a polyoxyalkylene bisphenol S and the like.

Examples of the aliphatic unsaturated polycarboxylic acid used for producing the above unsaturated polyester resin include (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and the like.

Examples of the aliphatic unsaturated polycarboxylic acid used for producing the unsaturated polyester resin include sebacic acid, adipic acid, (anhydrous) succinic acid and the like.

Examples of the aromatic polycarboxylic acid used for producing the unsaturated polyester resin include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride and endomethylenetetrahydrophthalic anhydride. It

The above-mentioned epoxy acrylate (vinyl ester) resin is usually prepared by a known and commonly used method.
It is produced from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

The epoxy resin used for producing the epoxy acrylate (vinyl ester) resin is also a bisphenol A type epoxy resin, epichlorohydrin and brominated bisphenol produced from epichlorohydrin and bisphenol A by a known and conventional method. Brominated bisphenol A type epoxy resin produced from A, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolac, glycidyl amine type epoxy resin obtained by reacting various amines with epichlorohydrin (tetraglycidyl Metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl p- aminophenol, triglycidyl -m- aminophenol, diglycidyl aniline, diglycidyl ortho-toluidine, etc.) and the like.

The urethane acrylate resin is usually
It is produced by reacting an organic polyol such as an alkylene diol, an alkylene diol ester, an alkylene diol ether, a polyether polyol or a polyester polyol with an organic polyisocyanate, and further reacting with a hydroxyalkyl (meth) acrylate.

As the polyol used for producing the urethane acrylate resin, alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, polyethylene glycol, polypropylene glycol, butane diol are used as polyether polyols. Is polyoxymethylene, polyethylene oxide,
Examples of polypropylene oxide include polyester polyols such as organic polyols such as alkylene diols and polycarboxylic acid condensation compounds.

Examples of the polyisocyanate used for producing the urethane acrylate resin include tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate and the like.

Examples of the hydroxylalkyl (meth) acrylate used for producing the urethane acrylate resin include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Is usually attached to the beta carbon of the alkyl group. Alkyl groups can usually contain up to 8 carbon atoms.

The diallyl phthalate resin is obtained by heating and polymerizing a diallyl phthalate monomer in the presence of a peroxide catalyst such as benzoyl peroxide to form a prepolymer.

The above melamine resin is obtained by condensing melamine and formaldehyde resin.

The above-mentioned phenol resin is obtained by reacting phenol alcohols with formalin. Two types are general-purpose: a resol type in which formaldehyde is excessive with respect to phenol and reacted with an alkali catalyst, and a novolac type in which formaldehyde is excessively reacted with an acid catalyst.

The thermosetting resin is usually styrene,
α-methylstyrene, divinylbenzene, vinyltoluene, diallyl phthalate, various acrylate monomers,
An appropriate amount of a polymerizable monomer such as various methacrylate monomers is added.

Among them, styrene and methyl methacrylate are preferably used because they are excellent in price and various performances.

If necessary, an organic peroxide as a radical reaction initiator can be used in the thermosetting resin. Specifically, for example, ketone peroxides such as methyl ethyl ketone peroxide, diacyl peroxides such as isobutyryl peroxide, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, and tertiary Alkyl peresters such as butyl peroxy-2-ethylhexanoate, carbonates such as tertiary butyl peroxy isopropyl carbonate, peroxy ketals such as 1,1-dibutyl peroxycyclohexane, etc. Has
Tertiary butyl peroxy benzoate, tertiary butyl peroxy isopropyl carbonate, etc. can be used.

Examples of the inorganic filler which is another constituent of the thermosetting resin composition with which the decorative base material is impregnated include the following. That is, halogenated minerals such as rock salt and potassium rock salt, carbonate minerals such as calcium carbonate, phosphate minerals such as cyanite, vanadate minerals such as carnotite, barite (barium sulfate), gypsum (calcium sulfate) Sulfate minerals such as borax, borate minerals such as borax, titanate minerals such as perovskite, mica, talc (talc), pyrophyllite, kaolin, silicate minerals such as quartz and feldspar, titanium oxide, Natural or artificial minerals centered on steel balls (aluminum oxide), metal (hydr) oxides such as aluminum hydroxide, glass products such as (hollow) glass spheres, etc., or treated
Purified or processed products and mixtures thereof are used.

The main uses of the inorganic filler are as follows. For example, there is a case where an inorganic filler is blended as an antifriction material in order to improve the abrasion resistance of the product surface. In such a case, silica, alumina, (hollow) glass spheres, etc. are preferably used. In addition, an inorganic filler may be blended in order to adjust the gloss of the product surface. In such a case, calcium carbonate, barium sulfate, talc, kaolin, aluminum hydroxide or the like is preferably used.

The amount of the inorganic filler added is preferably 0.5 to 60 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the resin content. If the addition amount is too small, it is difficult to obtain the effect of adding a sufficient inorganic filler for the improvement of abrasion resistance or the adjustment of gloss, and if it is too large, the viscosity of the thermosetting resin composition is high. Since it becomes too much, it becomes difficult to impregnate this with the substrate, which is not preferable in any case.

In the present specification, the term "resin content" means the total amount of components that can be chemically reacted into a resin such as a copolymerizable monomer in addition to a thermosetting resin such as an unsaturated polyester and a thermoplastic resin. Means

The average particle size of the inorganic filler is preferably 0.1 to 30 μm, more preferably 0.3 to 1
0 μm. If the particle size is too large, it becomes difficult to disperse the particles, and if it is too small, the viscosity of the composition mixed with the thermosetting resin becomes too high, and the base material is impregnated with this. This is not preferable in either case, which makes things difficult.

As the coupling agent which is another component of the thermosetting resin composition with which the decorative base material is impregnated, for example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent may be used. Can be used.

As the silane coupling agent, known and conventional ones are used. Specifically, as a trialkoxysilane compound, γ-(-2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, γ-chloropropyltrimethoxysilane, N-(-3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3
-Acryloxypropyltrimethoxysilane, 3-methacryloxypropenyltrimethoxysilane, 2-methacryloxyethyldimethyl [3-trimethoxysilylpropyl] ammonium chloride, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltri There are ethoxysilane and the like, dialkoxysilane compounds include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinylmethyldiethoxysilane and the like, and monoalkoxysilane compounds are present. , 3-acryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldimethylethoxysilane, vinyldimethylethoxysilane and the like.

Examples of the titanate coupling agent include isopropyl trioctanoyl titanate,
Isopropyl isostearyl diacryl titanate,
Tetra (2,2-diallyloxymethyl-1-butyl)
Bis (ditridecyl) phosphite titanate, isopropyl triisostearoyl titanate, isopropyl tri- (N-aminoethyl-aminoethyl) titanate, isopropyl trioctanoyl titanate and the like are used.

As the aluminum-based coupling agent, ethyl acetoaluminum diisopropylate, alkyl acetoacetate aluminum diisopropylate, etc. are used.

Among the above three types of coupling agents, the silane coupling agent is excellently used in terms of cost and performance, and is preferably used. Among them, the trialkoxysilane compound is preferably used because it is excellent in the adhesion improving effect.

The amount of the coupling agent used is
0.1 to 100 parts by weight of the resin component of the thermosetting resin composition
-20 parts by weight is preferable, and 0.5-7 parts by weight is more preferable. If the addition amount is too small, it is difficult to obtain a sufficient heat resistance improving effect. On the contrary, if the addition amount is too large, the viscosity of the composition becomes too low, which makes the decorative molding sheet sticky and difficult to handle. Is also not preferable.

A solvent, a monomer and the like are added to the above thermosetting resin composition, if necessary. For example, in the case of a resin having a high viscosity, a solvent or the like is added to improve the impregnating property and the viscosity is lowered. Further, in a resin having low reactivity, a monomer or the like can be added to improve the reactivity. When a solvent is used to reduce the viscosity, if it remains, it tends to cause defects such as bubbles during molding. Therefore, a step of volatilizing and drying the solvent after impregnating the resin is required.

Further, the above various thermosetting resin compositions include
If necessary, a polymerization inhibitor such as parabenzoquinone, an internal mold release agent such as zinc stearate, an antifungal agent and an antiseptic agent may be added in appropriate amounts.

Here, the amount of the thermosetting resin composition impregnated into the decorated base material is approximately when the base material made of an organic material such as paper, cloth or non-woven fabric is used. It is preferable to add 20 to 70% by weight, more preferably 30 to 70% by weight, based on the total weight after drying.
60% by weight.

Here, as the base material, glass cloth,
When an inorganic material such as a glass mat is used, it is approximately 10 with respect to the total weight of the impregnated sheet after drying.
It is preferable that it is blended so as to be about 50% by weight,
More preferably, it is 20 to 40% by weight.

The resin can be impregnated into the base material by a conventionally known method. That is, for example, a method in which the base material is immersed in the resin in the impregnation tank to impregnate the resin, the base material is pressed by a roll or the like to remove excess resin, and dried in a drying furnace as necessary, or There is a method of flowing a base material on a belt, placing a resin on the base material, and pressing the base material with a roll or a blade.

Next, the thermosetting molding material will be described. In the present invention, as the thermosetting molding material, those conventionally used as various thermosetting molding materials such as SMC and BMC can be used.

An example of preparation of the thermosetting molding material is as follows. That is, an unsaturated polyester resin, an epoxy acrylate resin, a urethane acrylate resin or the like is used as the thermosetting resin, and if necessary, an inorganic filler,
Reinforcing materials, additives, etc. are added, and by a conventionally known method,
A thermosetting resin composition having a form such as SMC or BMC is prepared.

The thermosetting resin used for preparing the thermosetting molding material may be the same as that used for preparing the decorative laminating sheet. The thermosetting resin is as described in detail in the description of the decorative laminating sheet.

Like the thermosetting resin for the decorative laminating sheet, the molding material is usually styrene, α-methylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, various methacrylate monomers, etc. An appropriate amount of polymerizable monomer is added.

Among them, styrene and methyl methacrylate are preferably used because they are excellent in price and various performances.

Further, the molding material includes, as a low-shrinking agent, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene-vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene, saturated polyesters, saturated polyester. A thermoplastic resin such as polyethers may be added in an appropriate amount as needed.

When the above thermoplastic resin is used, its amount is 0.1 to 30% by weight of the resin content.
Is preferable, and more preferably 0.3 to 20% by weight. If the amount used is too large, the viscosity of the molding material becomes high, so that it is difficult to obtain sufficient fluidity during molding, and if it is too small, it is difficult to obtain a sufficient shrinkage improving effect. Is also not preferable.

If desired, an organic peroxide as a radical reaction initiator may be used in the molding material. Specific examples of the organic peroxide are the same as those mentioned in the description of the thermosetting resin composition for a decorative laminate sheet.

When the above various copolymerizable monomers are used, the amount thereof is 1 to 70% by weight based on the resin content.
Is preferable, and more preferably 3 to 50% by weight.
It is. If the amount used is too small, the viscosity of the molding material becomes high, so sufficient fluidity cannot be obtained during molding,
On the other hand, if the amount is too large, the adhesiveness tends to decrease, which is not preferable in any case.

When the above organic peroxide is used, its amount is 0.3 to 5 parts by weight based on 100 parts by weight of the sum of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. Part is preferred, and more preferably 0.5 to
3 parts by weight. If the amount used is small, the curing speed of the molding material tends to be slow, and conversely, if the amount is too large, the molding material tends to yellow during curing, which is not preferable.

Further, an appropriate amount of inorganic filler can be added to the molding material depending on the purpose and application. Examples of usable inorganic fillers include elemental minerals such as graphite and diamond in addition to those exemplified above as the inorganic filler constituting the thermosetting resin composition with which the decorative base material is impregnated.

Further, a coloring pigment can be used in an appropriate amount in the molding material, if necessary. A conventionally known pigment is used as the color pigment. For example, titanium oxide, benzine yellow, anthraquinone yellow, titanium yellow, Hansa yellow, molybdate orange,
Yellow lead, disazo yellow, benzine orange, quinacridone red, quinacridone magenta, naphthol violet, chrome green, phthalocyanine green, alkali blue, cobalt blue, phthalocyanine blue, iron oxide (red iron oxide), copper azo brown, aniline black, carbon black, iron Various well-known and commonly used ones such as black, aluminum flakes, nickel powder, gold powder, silver powder and the like are used.

Among them, titanium oxide, titanium yellow, quinacridone red, quinacridone magenta, phthalocyanine blue, iron oxide (red iron oxide), carbon black,
Iron black, aluminum flakes and the like are preferably used because they have little influence on the curability of the molding material.

The addition amount of the color pigment used in the molding material is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the resin component. Further, the addition amount of the inorganic filler is preferably 0 to 300 parts by weight, and more preferably 0 to 250 parts by weight with respect to 100 parts by weight of the resin content.
The total amount of the color pigment and the inorganic filler is preferably 30 to 320 parts by weight, more preferably 40 to 2 parts by weight.
It is adjusted to be 00 parts by weight. If the addition amount of the inorganic filler and the color pigment is too small, it is difficult to obtain sufficient hiding property, and if the addition amount is too large, the viscosity of the composition becomes high, so that sufficient fluidity in the mold at the time of molding is obtained. Is difficult to obtain, and in any case, it is not preferable.

As a reinforcing material, various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added to the molding material in appropriate amounts.

When reinforcing fibers are used as the molding material, the amount of the reinforcing fibers used is 1-100 with respect to the resin content.
It is preferable to set it as a weight part, More preferably, it is 3-90.
It is Shibube. If the amount used is too small, it is difficult to obtain a sufficient reinforcing effect. On the contrary, if the amount is too large, the viscosity of the composition becomes high, so it is difficult to obtain sufficient fluidity in the mold during molding. Either case is not preferable.

Furthermore, if necessary, the molding material may include
Dimethylaniline, known curing accelerators such as cobalt naphthenate, polymerization inhibitors such as parabenzoquinone, azo dyes and anthraquinones, indigoids, dyes such as stilbene, conductivity imparting agents such as carbon black, emulsifiers,
A metal soap such as zinc stearate, an aliphatic phosphate, a release agent such as lecithin and the like can be added in an appropriate amount depending on the use and purpose.

The preferred embodiment of the present invention is as follows. More specifically, the molding material used in the present invention is, for example, an unsaturated polyester resin liquid (styrene concentration 4
0 to 70% by weight) 60 to 100 parts by weight of styrene solution such as polystyrene resin (styrene concentration 40 to 70% by weight)
Add 0 to 40 parts by weight to 100 parts by weight, and add 60 to 160 parts by weight of inorganic filler such as calcium carbonate, aluminum hydroxide, glass powder, titanium oxide, iron oxide, carbon black, titanium yellow, etc. Pigment 5-20
7 parts by weight, 0.7 to 2.5 parts by weight of organic peroxide such as tertiary butyl peroxybenzoate, and 0.5 to 3 parts by weight of a thickener such as magnesium oxide, for a total of 7 inorganic components.
A compound in which 0 to 180 parts by weight is added is kneaded to form a compound, and 5 to 18 parts by weight of a reinforcing material such as glass fiber is impregnated into a compound, which is preferably used in the form of SMC or BMC.

Next, the invention according to claim 2 will be described.

In the second aspect of the invention, the thermosetting resin composition with which the decorative base material is impregnated contains an inorganic filler surface-treated with a coupling agent. As a method of surface-treating the inorganic filler with a coupling agent, there are the following methods. For example, a simple method is to prepare a pure coupling agent solution or an aqueous solution or alcohol solution of the coupling agent, immerse the inorganic filler in the solution, then pull it up and dry it at room temperature or high temperature.

In the invention described in claim 2, the addition amounts of the inorganic filler and the coupling agent used are the same as the values described in the invention described in claim 1.

The other structure of the invention described in claim 2 is the same as that described in the invention described in claim 1.

Next, the invention according to claim 3 will be described.

The method for producing a decorative molded article according to the invention of claim 3 is carried out using the decorative laminating sheet of claim 1 or 2, and the specific operation is as follows.

As the molding machine used in the present invention, a conventionally known press molding machine can be used. Further, as the molding die, conventionally known dies, casting dies and the like can be used.

As the mold type, generally, the upper and lower molds are preferably used. In this case, the upper mold is usually used as a movable mold and the lower mold as a fixed mold.

The above mold is attached to the above molding machine,
After heating to 80 to 180 ° C., with the mold opened, the decorative laminating sheet that is the material to be compressed and the molding material are placed at the required positions in an overlapping manner.

After closing the mold in this way,
When pressure molding is performed at a pressure of 120 kg / cm @ 2 for 30 seconds to 15 minutes to cure the object to be molded, the mold is opened and the product is demolded to obtain a laminated decorative molded product.

Regarding the direction of the decorative surface of the decorative laminating sheet in the molding die, it is common to orient the decorative surface toward the molding die so that the surface of the obtained molded product comes to the decoration surface. However, the decorative surface may be directed to the molding material side, if necessary.

Here, the size of the decorative laminating sheet may be large so that the entire surface of the molded product is decorated with it, or small so that only a part of the surface of the molded product is decorated. It doesn't matter. That is, a decorative laminating sheet having an arbitrary size and shape is used according to the desired design.

If necessary, a glass mat, a glass cloth, or a glass cloth may be provided between the decorative laminating sheet and the molding material.
A cloth, a non-woven cloth, or a material obtained by impregnating these with a resin may be laminated as an intermediate layer.

Next, the invention according to claims 4 and 5 will be described.

The invention according to claim 4 is a method for producing a decorated molded article, characterized in that a thermosetting resin composition containing a coupling agent is used as the thermosetting molding material. The invention of Item 5 uses a thermosetting resin composition containing a coupling agent as a thermosetting molding material, and a thermosetting resin composition containing a coupling agent as a decorative laminating sheet. A method for producing a decorated molded product, which comprises using a product obtained by impregnating a decorated base material.

In the method for producing a decorated molded article according to claims 4 and 5, a coupling agent contained in a thermosetting resin composition used as a molding material, and the method for producing a decorated molded article according to claim 5. The coupling agent contained in the thermosetting resin composition with which the decorative base material is impregnated is as described in the section of the invention of claim 1.

In Claims 4 and 5, the decorative laminating sheet of Claims 1 and 2 can be used as the decorative laminating sheet, but the inorganic filler used in Claims 1 and 2 is not necessarily required. Not an essential ingredient. Further, the coupling agent is not essential for the decorative laminating sheet according to claim 4.

In the method for producing a decorated molded article according to claims 4 and 5, the amount of the coupling agent contained in the thermosetting resin composition used as the molding material is the resin component of the thermosetting resin composition. 0.1 to 60 per 100 parts by weight
Part by weight is suitable, and more preferably 0.3 to 25 parts by weight. If the amount added is too small, it is difficult to obtain a sufficient adhesion improving effect, and if the amount added is too large, the strength of the molded product tends to decrease, which is not preferable.

In the method for producing a decorated molded article according to 5,
The amount of the coupling agent contained in the thermosetting resin composition with which the decorative base material is impregnated is preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the resin component of the thermosetting resin composition. Yes, more preferably 0.5 to 30 parts by weight. If the addition amount is too small, it is difficult to obtain a sufficient adhesiveness improving effect, and if the addition amount is too large, the viscosity of the composition becomes too low, which makes the decorative molding sheet sticky and difficult to handle. Is also not preferable.

The difference between the invention described in claim 4 and the invention described in claim 5 will be described. The difference between these inventions is whether or not the decorative laminating sheet contains a coupling agent. Of course, when the decorative laminating sheet contains a coupling agent, the adhesiveness of the decorative laminating sheet to the molded product is remarkably improved. Is preferred. However, the coupling agent is an expensive material, and the increase in material cost cannot be avoided by using this, so for products that do not require very strict durability as the environment in which the product is used, do not use the coupling agent, It is preferable to carry out the invention according to claim 4. Even in this case, of course, a significant improvement effect of adhesion can be obtained compared to the conventional one. Therefore, in reality, it depends on how strict the usage environment of the product is required and the cost. The invention according to claim 4 or the invention according to claim 5 is implemented.

Since the present invention is constructed as described above,
The following effects are exhibited. In the invention of claim 1, the decorative laminating sheet contains an inorganic filler and a coupling agent, and in the invention of claim 2, the decorative laminating sheet has an inorganic filler surface-treated with a coupling agent. Therefore, when compression molding is performed using such a decorative laminate sheet, the hydrolyzable group of the coupling agent forms a chemical bond with the surface of the inorganic filler, and the hydrophobic group is a molding material. And has a chemical bond with the thermosetting resin composition. Therefore, the adhesive force between the inorganic filler and the molding material is improved through the coupling agent, and as a result, when the product is exposed to hot water, the filler powder is detached from the surface and the whitening phenomenon occurs. Hot water resistance is significantly improved.

Further, in the manufacturing method of the invention as claimed in claim 4, since the molding material contains a coupling agent, the polar group density of the thermosetting resin composition in the molding material is increased, and therefore, for decoration. Many hydrogen bonds are formed with the sheet, which improves the adhesion between the decorative laminating sheet and the molding material.

In the manufacturing method of the fifth aspect of the present invention, both the decorative laminating sheet and the molding material contain a coupling agent, whereby the coupling agent in the decorative laminating sheet and the cup in the molding material are contained. The ring agent causes a chemical reaction at the interface to generate a large number of chemical bonds, which significantly improves the adhesion between the decorative laminating sheet and the molding material.

[0100]

Embodiments of the present invention will be described below. 1. Preparation of Molding Machine and Mold As the molding machine, a 300-ton press molding machine manufactured by Kawasaki Yuko Co., Ltd. was used.

As a mold, a mold for molding a 30 cm × 30 cm square flat plate was prepared.

The upper mold and the lower mold both have an electric heater and a cooling water pipe embedded therein. This mold was attached to the above press molding machine. The upper mold was a movable mold and the lower mold was a fixed mold.

2. Preparation of Decorative Laminating Sheet The decorative laminating sheet was prepared as follows. 1) Preparation of resin solution for impregnation Resin solution for impregnation 1 (1) Unsaturated polyester resin (number average molecular weight of about 2000
(1) Dissolved isophthalic unsaturated polyester resin in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Silane coupling agent ( γ-methacryloxypropyltrimethoxysilane) 1 part by weight (4) Alumina powder (average particle size of about 5 μm) 15 parts by weight The above components (1) to (4) are mixed and sufficiently stirred to obtain a resin solution for impregnation. It was set to 1.

Impregnating Resin Liquid 2 (1) Diallyl phthalate resin (a diallyl phthalate resin having a number average molecular weight of about 700 dissolved in a diallyl phthalate monomer, a diallyl phthalate monomer concentration of 45)
%) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Silane coupling agent (γ-glycidoxypropyltrimethoxysilane) 7 parts by weight (4) Silica powder ( 10 parts by weight of average particle size of about 2 μm) The components (1) to (4) described above were mixed and sufficiently stirred to prepare a resin solution 2 for impregnation.

Impregnating Resin Liquid 3 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid type unsaturated polyester resin of styrene, concentration of styrene is 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Titanate coupling agent (Isopropyltrioctanoyl titanate) 3 parts by weight (4) Calcium carbonate powder (average particle size of about 1 μm) 10 parts by weight The above components (1) to (4) are mixed and sufficiently stirred, and the impregnating resin liquid 3 is added. And

Impregnating Resin Liquid 4 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid type unsaturated polyester resin of styrene dissolved in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Aluminum coupling agent (Ethyl acetoacetate aluminum diisopropylate) 5 parts by weight (4) Alumina powder (average particle size of about 0.5 μm) 1 part by weight The components (1) to (4) above are mixed, sufficiently stirred, and impregnated. Resin solution 4 was used.

Resin solution for impregnation 5 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid-based unsaturated polyester resin of styrene, concentration of styrene 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Silane coupling agent Surface-treated alumina powder (alumina powder having an average particle size of about 5 μm is a silane coupling agent (γ-glycidoxypropyltrimethoxysilane))
15 parts by weight of the above components (1) to (3) were mixed and sufficiently stirred to prepare a resin solution 5 for impregnation. .

Impregnating Resin Liquid 6 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid-based unsaturated polyester resin of styrene, concentration of styrene is 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Titanium coupling agent Carbonate surface-treated calcium carbonate powder (a calcium carbonate powder having an average particle size of about 1 μm was immersed in a 10 wt% alcohol solution of a titanate coupling agent (isopropyl trioctanoyl titanate) and then dried at 80 ° C. for 2 hours. ) 10 parts by weight The above components (1) to (3) were mixed and sufficiently stirred to obtain a resin solution 6 for impregnation.

Resin solution for impregnation 7 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid type unsaturated polyester resin of styrene dissolved in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Aluminum coupling agent The surface-treated silica powder (silica powder having an average particle size of about 0.5 μm was dipped in a 10 wt% alcohol solution of an aluminum coupling agent (ethyl acetoacetate aluminum diisopropylate) and then dried at 80 ° C. for 2 hours. 2 parts by weight The above components (1) to (3) were mixed and sufficiently stirred to obtain a resin solution for impregnation 7.

Resin solution for impregnation 8 (1) Unsaturated polyester resin (number average molecular weight of about 2000
100 parts by weight of a styrene concentration of 40% by weight of an isophthalic unsaturated polyester resin dissolved in styrene (2) 1 part by weight of a polymerization initiator (tertiary butyl peroxybenzoate) (3) Calcium carbonate powder (average) 10 parts by weight (particle size: about 1 μm) The components (1) to (3) above were mixed and sufficiently stirred to prepare a resin solution 8 for impregnation.

Impregnating Resin Liquid 9 (1) Diallyl phthalate resin (a diallyl phthalate resin having a number average molecular weight of about 700 dissolved in a diallyl phthalate monomer, a diallyl phthalate monomer concentration of 45)
% By weight) 100 parts by weight (2) 1 part by weight of a polymerization initiator (tertiary butyl peroxybenzoate) The components (1) and (2) above were mixed and sufficiently stirred to prepare a resin solution 9 for impregnation.

Resin solution for impregnation 10 (1) Unsaturated polyester resin (number average molecular weight of about 2000
(1) Dissolved isophthalic unsaturated polyester resin in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Silane coupling agent ( (γ-methacryloxypropyltrimethoxysilane) 1 part by weight The components (1) to (3) above were mixed and sufficiently stirred to prepare a resin solution 10 for impregnation.

Resin solution for impregnation 11 (1) Diallyl phthalate resin (a diallyl phthalate resin having a number average molecular weight of about 700 dissolved in a diallyl phthalate monomer, a diallyl phthalate monomer concentration of 45)
% By weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Silane coupling agent (γ-glycidoxypropyltrimethoxysilane) 7 parts by weight Above (1) to ( The components of 3) were mixed and sufficiently stirred to obtain a resin solution 11 for impregnation.

Resin solution for impregnation 12 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid type unsaturated polyester resin of styrene, concentration of styrene is 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Titanate coupling agent (Isopropyltrioctanoyl titanate) 3 parts by weight The components (1) to (3) above were mixed and sufficiently stirred to prepare a resin solution 12 for impregnation.

Resin solution for impregnation 13 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of isophthalic acid type unsaturated polyester resin of styrene dissolved in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (3) Aluminum coupling agent (Ethyl acetoacetate aluminum diisopropylate) 5 parts by weight The components (1) to (3) described above were mixed and sufficiently stirred to obtain a resin solution 13 for impregnation.

Impregnating Resin Liquid 14 (1) Unsaturated polyester resin (number average molecular weight of about 2000
Of an isophthalic acid-based unsaturated polyester resin of styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (1) to (2) above The above components were mixed and sufficiently stirred to obtain a resin liquid 14 for impregnation.

2) Preparation of Decorative Base Material Decorative Base Material 1 Titanium paper (thickness 0.1 mm, basis weight 80 g / m ² , PM1)
1P: manufactured by Kojin Co., Ltd. with a black granite pattern printed on it Decorative base material 2 Nylon cloth (thickness 0.1 mm, basis weight 90 g / m ² , manufactured by Toyobo Co., Ltd.) black granite pattern Printed with stone pattern Decorative base material 3 Nonwoven fabric made of polyester (thickness 0.36 mm, basis weight 40.
7g / m ² , Sontara # 8000: manufactured by DuPont Toray Co., Ltd., printed with a black granite stone pattern Decorative base material 4 glass cloth (thickness 0.25 mm, basis weight 200 g /
m ^2, plain weave, WF230100BS6: Nitto Boseki Co., Ltd.) to those that have been printing the pebbled pattern of black granite tone Kakazarimotozai 5 glass mat (with a thickness of 0.41mm, a basis weight of 60g / m ^2,
SM3603E: manufactured by Asahi Fiber Glass Co., Ltd., with a black granite-tone stone pattern printed on it 3) Preparation of a decorative laminating sheet Decorative laminating sheet 1 A decorative base material 1 is cut into a size of 20 cm × 20 cm, After this cut piece is immersed in the impregnating resin liquid 1 to impregnate the resin, the cut piece is pressed with a roll to remove excess resin,
A decorative laminating sheet 1 was obtained. The weight ratio of the base material (titanium paper) in this decorative laminating sheet was 45% by weight.

Decorative Laminating Sheet 2 to 32 Decorative laminating sheet 2 in the same manner as decorative laminating sheet 1 except that the decorative base material and impregnating resin are used in the combinations shown in Tables 1 to 7 below. ~ 32. The weight ratio of the base material in these decorative laminating sheets 2 to 32 is shown in Tables 1 to 7.

3. Preparation of molding material The following colored molding material was used as a molding material. Molding material 1 (1) Unsaturated polyester resin liquid (number average molecular weight about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) 70 parts by weight of glass fiber (roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm)

Of the above-mentioned compounding materials, the compounding materials (1) to (7) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (8) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
A molding material 1 was obtained.

Molding Material 2 (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) 5 parts by weight of silane coupling agent (γ-methacryloxypropyltrimethoxysilane) (9) 70 parts by weight of glass fiber (Roving made by Asahi Fiber Glass: ER4630LBD166W cut into a length of 25 mm)

Of the above-mentioned compounding materials, the compounding materials (1) to (8) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (9) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
Molding material 2 was obtained.

Molding Material 3 (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) Titanate coupling agent (isopropyl trioctanoyl titanate) 3 parts by weight (9) Glass fiber (Roving made by Asahi Fiber Glass: ER4630LBD166W cut into a length of 25 mm) 70 parts by weight

Of the above-mentioned compounding materials, the compounding materials (1) to (8) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (9) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
A molding material 3 was obtained.

Molding Material 4 (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) Aluminum coupling agent (ethyl acetoacetate aluminum diisopropylate) 1 part by weight (9) Glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm) 70 parts by weight

Of the above-mentioned compounding materials, the compounding materials (1) to (8) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (9) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
A molding material 4 was obtained.

Molding material 5 (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) 2 parts by weight of silane coupling agent (γ-methacryloxypropyltrimethoxysilane) (9) 70 parts by weight of glass fiber (Roving made by Asahi Fiber Glass: ER4630LBD166W cut into a length of 25 mm)

Of the above-mentioned compounding materials, the compounding materials (1) to (8) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (9) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
A molding material 5 was obtained.

4. Molding Method A decorative molded product was molded as follows from the decorative laminating sheet and the molding material thus obtained.

Example 1 After heating the upper mold to 140 ° C. and the lower mold to 150 ° C., the decorative laminating sheet 1 was placed on the lower mold as the decorative laminating sheet.
Two pieces of the molding material 1 cut into a size of 20 cm × 20 cm were charged thereon. 10 after closing the mold
Pressure molding was performed for 240 seconds at a pressure of 0 kg / cm ² .
Then, the mold was opened and demolded to obtain a decorative molded product. As shown in the attached FIGS. 1 to 3, a molded article having a desired shape can be obtained depending on the sizes of the decorative laminating sheet (11) and the molding layer (12) made of a colored molding material.

Examples 2 to 42, Comparative Examples 1 to 15 Molding was performed in the same manner as in Example 1 except that the decorative laminating sheets and molding materials shown in Tables 1 and 7 were used.

[0132] 5. Evaluation Method The molded articles obtained in the above Examples and Comparative Examples were subjected to evaluation tests of the following items.

1) Appearance after hot water treatment 10 cm × 10 cm test pieces were cut out from the molded articles obtained in Examples 1 to 12 and Comparative Examples 1 to 6 and immersed in hot water at 80 ° C. for 24 hours. After that, the surface water was wiped off, and after leaving for 2 hours, the change in the surface color tone was observed.

The results of the above test are shown in Tables 1 to 3. As is clear from these tables, the products obtained in the examples were good ones with little change in color tone, but all the products obtained in the comparative examples were significantly whitened and were completely different from the original color tone. It was a thing.

2) Initial Adhesion Test Initial adhesion of the molded articles obtained in Examples 13 to 42 and Comparative Examples 7 to 15 was measured. That is, using a cutter knife on the surface of the molded product, that is, a decorative surface, 11 straight lines were drawn at 2 mm intervals so as to reach the substrate, and 11 straight lines orthogonal to these straight lines were drawn to obtain the board. After sticking an adhesive tape (cellophane tape manufactured by Sekisui Chemical Co., Ltd.) on the eye-shaped portion, the adhesive tape was peeled off, and the number of remaining grids was examined (cross-grid adhesion test, initial adhesion evaluation).

3) Adhesion test 1 after hot water treatment 1 10 cm × 10 cm test pieces were cut out from the molded articles obtained in Examples 13 to 42 and Comparative Examples 7 to 15, and these were placed in hot water at 60 ° C. After soaking for 24 hours, water on the surface was wiped off, and after leaving for 2 hours, the same adhesion test as above was performed (secondary adhesion evaluation).

4) Adhesion test 2 after hot water treatment Further, 10 cm × 10 cm test pieces were cut out from the molded articles obtained in Examples 13 to 42 and Comparative Examples 7 to 15 and heat-treated at 90 ° C. After soaking in water for 24 hours, the water on the surface was wiped off, and after leaving for 2 hours, the same adhesion test as described above was performed (secondary adhesion evaluation).

The results of the above tests 1) to 3) are shown in Tables 4 to 7. As is clear from these tables, the products obtained in the examples had good adhesion, but the products obtained in the comparative examples had poor adhesion.

[0139]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[0140]

According to the invention of claim 1, the decorative laminating sheet contains an inorganic filler and a coupling agent, and in the invention of claim 2, the decorative laminating sheet is surface-treated by the coupling agent. Since it contains a treated inorganic filler, when compression-molding is performed using such a decorative laminating sheet, the hydrolyzable group of the coupling agent forms a chemical bond with the surface of the inorganic filler and also has a hydrophobic property. The functional group has an affinity with the thermosetting resin composition of the molding material or forms a chemical bond. Therefore, the adhesive force between the inorganic filler and the molding material is improved through the coupling agent, and as a result, when the product is exposed to hot water, the filler powder is detached from the surface and the whitening phenomenon occurs. Hot water resistance is significantly improved.

Further, in the manufacturing method of the invention as claimed in claim 4, since the molding material contains a coupling agent, the polar group density of the thermosetting resin composition in the molding material is increased, and therefore, for decoration. Many hydrogen bonds are formed with the sheet, which improves the adhesion between the decorative laminating sheet and the molding material.

In the manufacturing method of the fifth aspect of the present invention, both the decorative laminating sheet and the molding material contain a coupling agent, whereby the coupling agent in the decorative laminating sheet and the cup in the molding material are contained. The ring agent causes a chemical reaction at the interface to generate a large number of chemical bonds, which significantly improves the adhesion between the decorative laminating sheet and the molding material.

According to the present invention, according to the present invention, the adhesiveness of the decorative laminating sheet to the molded product can be improved when molding the decorative laminating sheet laminated molded product having a design such as a free pattern or color. It is possible to provide a method for producing a decorative molded article which is excellent in heat resistance and hot water resistance, and a decorative laminating sheet used for obtaining such a good decorative molded article.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing an example of a molded product obtained by the present invention.

FIG. 2 is a vertical cross-sectional view showing another example of the molded product obtained by the present invention.

FIG. 3 is a vertical sectional view showing still another example of the molded product obtained according to the present invention.

[Explanation of symbols]

 (11): Decorative laminated sheet (12): Molding material

Claims (5)

[Claims] 1. A decorative laminating sheet, characterized in that a decorative base material is impregnated with a thermosetting resin composition containing an inorganic filler and a coupling agent. 2. A decorative laminating sheet characterized in that a decorative base material is impregnated with a thermosetting resin composition containing an inorganic filler surface-treated with a coupling agent. 3. The decorative laminating sheet according to claim 1 or 2 is used as the decorative laminating sheet when the decorative laminating sheet is laminated on a thermosetting molding material and the molding material is subjected to heat compression molding. A method for producing a decorated molded article, which is characterized by the following. 4. A thermosetting molding material containing a coupling agent as a thermosetting molding material for placing a decorative laminating sheet on a thermosetting molding material in a laminated state and performing heat compression molding of the molding material. A method for producing a decorated molded article, which comprises using a resin composition. 5. A thermosetting molding material containing a coupling agent as a thermosetting molding material, when the decorative laminating sheet is laminated on a thermosetting molding material and the molding composition is subjected to heat compression molding. Production of a decorative molded article characterized by using a resin composition, and using as a decorative laminate sheet, a decorative base material impregnated with a thermosetting resin composition containing a coupling agent. Method.